Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Reaction of Tertiary 2-Chloroketones with Cyanide Ions: Application to 3-Chloroquinolinediones.

ABSTRACT: 3-Chloroquinoline-2,4-diones react with cyanide ions in dimethyl formamide to give 3-cyanoquinoline-2,4-diones in small yields due to the strong hindrance of the substituent at the C-3 atom. Good yields can be achieved if the substituent at this position is the methyl group. In the methanol solution, the reaction proceeds by an addition mechanism to form 2-oxo-1a,2,3,7b-tetrahydrooxireno[2,3-c]quinoline-7b-carbonitriles, from which 4-hydroxy-3-methoxy-2-oxo-1,2,3,4-tetrahydroquinoline-4-carbonitriles are subsequently formed by opening of the epoxide ring with methanol. Some minor products of these reactions have also been isolated. The ¹ H, ¹³ C and ¹⁵ N NMR spectra of the prepared compounds were measured, and all resonances were assigned using appropriate two-dimensional spectra.

SUBMITTER: Klasek A

PROVIDER: S-EPMC8202728 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Reaction of Tertiary 2-Chloroketones with Cyanide Ions: Application to 3-Chloroquinolinediones.

Klásek Antonín A Kafka Stanislav S Rudolf Ondřej O Lyčka Antonín A Rouchal Michal M Bednář Lukáš L

ChemistryOpen 20210601 6

3-Chloroquinoline-2,4-diones react with cyanide ions in dimethyl formamide to give 3-cyanoquinoline-2,4-diones in small yields due to the strong hindrance of the substituent at the C-3 atom. Good yields can be achieved if the substituent at this position is the methyl group. In the methanol solution, the reaction proceeds by an addition mechanism to form 2-oxo-1a,2,3,7b-tetrahydrooxireno[2,3-c]quinoline-7b-carbonitriles, from which 4-hydroxy-3-methoxy-2-oxo-1,2,3,4-tetrahydroquinoline-4-carbonit ...[more]

PMID: 34126002

Similar Datasets

Extending the Chemistry of Reaction between BODIPY and Cyanide Ions: An Application in Selective Sensing of Fluoride and Cyanide Ions.

Project description:A novel colorimetric BODIPY-based probe for selective detection of fluoride and cyanide has been developed. The color of the solution significantly changes upon addition of fluoride and cyanide ions with detection limits of 2.2 × 10-7 and 1.8 × 10-7 M calculated by UV-vis absorption method for F- and CN- respectively. An unprecedented phenomenon about the interaction of cyanide ions with the probe was discovered which has not been reported yet. The green color of the paper strip in the presence of cyanide ions changes with time. This observation indicates that unlike fluoride, the cyanide ion interaction with the probe is beyond mere deprotonation of the phenolic group rather envisaged as nucleophilic addition reaction. The phenomenon was also observed in the solution phase and subsequently the reaction order and rate constant of the reaction were determined from absorption versus time graph which were found to be first order and 0.3465 s-1 respectively. The emission spectra also showed different behavior of interaction with time for the two ions. The rate of the reaction was found to be independent of the solvent polarity. The plausible mechanism of the reaction between cyanide and fluoride ions with the probe was proposed based on 1H NMR titration experiments and mass spectrometry.

| S-EPMC9774366 | biostudies-literature

Functionalized 2-Hydrazinobenzothiazole with Bithiophene as a Colorimetric Sensor for Lethal Cyanide Ions and Its Application in Food Samples.

Project description:A newly synthesized Schiff's base 2-(2-([2,2'-bithiophen]-5-ylmethylene)hydrazinyl)benzothiazole (BT) was obtained from the condensation reaction between 2-hydrazinobenzothiazole and 2,2-bithiophene-5-carboxaldehyde. The prepared probe BT was subjected to a confirmation of the structural arrangement through NMR, FTIR, ESI-HRMS, and single-crystal XRD spectral analysis. The BT colorimetric sensor showed selectivity and sensitivity toward the cyanide (CN-) ion over other common anions such as ClO4-, Cl-, Br-, F-, I-, NO2-, OH-, HSO4-, and H2PO4- in a partial aqueous system CH3CN/H2O (8:2, v/v). The probe BT detects CN- with the lowest detection range as low as 1.33 × 10-8 M (3.59 ppm); in comparison to that given by WHO guidelines, it is significantly lower. The stoichiometric interaction between the probe BT and analyte CN- was found to be 1:1 (BT/CN-) binding mode using Jobs plot, and further association binding affinity was calculated to be 6.64 × 10-3 M-1. Additionally, these results were further supported by the FTIR and DFT calculations, as well as the 1H NMR titration analysis, which complemented the binding data. The sensor probe BT was successfully employed in a cotton swab test kit approach and also in smartphone-assisted applications for the determination of CN- ions. Finally, the outstanding sensing properties of probe BT aided the quantitative detection of CN- ions, and it could be further applied to a variety of food samples, including apple seeds, sprouting potatoes, and cassava.

| S-EPMC10938305 | biostudies-literature

Highly Sensitive Ratiometric Chemosensor and Biomarker for Cyanide Ions in the Aqueous Medium.

Project description:A newly designed cyanide-selective chemosensor based on chromone containing benzothiazole groups [3-(2,3-dihydro-benzothiazol-2-yl)-chromen-4-one (DBTC)] was synthesized and structurally characterized by physico-chemical, spectroscopic, and single-crystal X-ray diffraction analyses. The compound DBTC can detect cyanide anions based on nucleophilic addition as low as 5.76 nM in dimethyl sulfoxide-N-(2-hydroxyethyl)piperazine-N'-ethanesulfonic acid buffer (20 mM, pH 7.4) (v/v = 1:3). The binding mode between receptor DBTC and cyanide nucleophile has also been demonstrated by experimental studies using various spectroscopic tools and theoretical studies, and the experimental work has also been verified by characterizing one supporting compound of similar probable structure of the final product formed between DBTC and cyanide ion (DBTC-CN compound) by single-crystal X-ray analysis for detailed structural analyses. In theoretical study, density functional theory procedures have been used to calculate the molecular structure and the calculation of the Fukui function for evaluation of the electrophilic properties of each individual acceptor atom. Furthermore, the efficacy of the probe (DBTC) to detect the distribution of CN- ions in living cells has been checked by acquiring the fluorescence image using a confocal microscope. Notably, the paper strips with DBTC were prepared, and these could serve as efficient and suitable CN- test kits successfully.

| S-EPMC6130900 | biostudies-literature

Quinoline based thiosemicarbazones as colorimetric chemosensors for fluoride and cyanide ions and DFT studies.

Project description:High toxicity and extensive accessibility of fluoride and cyanide ions in diverse environmental media encouraged attention for scheming well-organized probes for their detection. Keeping in mind we have designed and synthesized thiosemicarbazone-based chemosensors RB-1, RB-2 and RB-3 for the detection of fluoride and cyanide ions. The structural elucidation of the synthesized chemosensors is done by employing different analytical techniques including nuclear magnetic resonance and electronic absorption specrtoscopies. Admirable detection limit, binding constant and fast response time (2 s) to F- and CN- ions enlarged the applications of these chemosensors. Additional confirmation of the sensing ability of these chemosensors is derived from DFT and TDDFT calculations with M06/6-311G(d,p) method by performing FMO, UV-Vis, QTAIM and global reactivity parameters elucidation. Overall results point out that investigated chemosensors are suitable candidates for sensing the F- ions. These chemosensors were successfully applied to detect F- ions in a commercial toothpaste sample.

| S-EPMC8943172 | biostudies-literature

Synthesis of novel 3-hydroxy-2-naphthoic hydrazones as selective chemosensors for cyanide ions.

Project description:The development of an effective and selective chemosensor for CN- ions has become the need of the hour due to their hazardous impact on the environment and humans. Herein, we report the synthesis of two novel chemosensors, IF-1 and IF-2 based on 3-hydroxy-2-naphthohydrazide and aldehyde derivatives that have shown selective sensing of CN- ions. IF-2 exhibited exclusive binding with CN- ions that is further confirmed by the binding constant value of 4.77 × 104 M-1 with a low detection limit (8.2 μM). The chemosensory potential is attributed to deprotonation of the labile Schiff base center by CN- ions that results in a color change from colorless to yellow as visible by the naked eye. Accompanying this, a DFT study was also performed in order to find the interaction between the sensor (IF-1) and its ions (F-). A notable charge transfer from 3-hydroxy-2-naphthamide to 2,4-di-tert-butyl-6-methylphenol, was indicated by the FMO analysis. The QTAIM analysis revealed that in the complex compound, the strongest pure hydrogen-hydrogen bonding was observed between H53 and H58, indicated by a ρ value of +0.017807. Due to its selective response, IF-2 can be successfully used for making test strips for the detection of CN- ions.

| S-EPMC10193203 | biostudies-literature

A sensitive and selective BINOL based ratiometric fluorescence sensor for the detection of cyanide ions.

Project description:A highly selective, novel BINOL based sensor BBCN has been developed for the fluorescent ratiometric detection of cyanide ions (CN-). The optical study revealed that BBCN exhibited unique spectral changes only with cyanide ions in the presence of other competing ions. Besides, an apparent fluorescent colour change from green to blue was observed. A clear linear relationship was observed between the fluorescence ratiometric ratio of BBCN and the concentration of CN- with a reasonably low detection limit (LOD) of 189 nM (507 ppb). The optical response was due to the nucleophilic addition of CN- to the dicyanovinyl group of the sensor, which compromises the probe's intramolecular charge transfer. This mechanism was well confirmed by Job's plot, 1H-NMR and ESI-MS studies. BBCN showed immediate spectral response towards (1 second) CN- and detection could be realized in a broad pH window. Furthermore, the practical utility of BBCN was studied by test paper-based analysis and the detection of CN- in various water resources.

| S-EPMC9029250 | biostudies-literature

Efficient fluorescence-enhanced probe for cyanide ions based on a tetraphenylethene pyridine coordinated copper-iodide complex.

Project description:An efficient fluorescence-enhanced probe was developed for detecting cyanide ions (CN-) based on a tetraphenylethene coordinated copper-iodide complex (named CIT-Z). The coordination polymers (CPs) prepared were (Z)-1,2-diphenyl-1,2-bis[4-(pyridin-3-ylmethoxy)phenyl]ethene (1Z) and a CuI cluster, where the tetraphenylethylene (TPE) pyridine derivatives acted as organic ligands and the CuI cluster acted as a metal center. The higher-dimensional CIT-Z exhibited a 3-fold-interpenetrating network structure with excellent optical properties and chemical stability. This study also provides insights into the mechanism behind the fluorescence enhancement, which is attributed to the competitive coordination between CN- and the ligands. The probe showed high selectivity and sensitivity towards CN-, with a detection limit of 0.1 μM and good recovery in the real water samples.

| S-EPMC10312066 | biostudies-literature

Methoxyquinolone-Benzothiazole Hybrids as New Aggregation-Induced Emission Luminogens and Efficient Fluorescent Chemosensors for Cyanide Ions.

Project description:This work describes the synthesis and characterization of new quinolone-benzothiazole hybrids, the study of their aggregation-induced emission (AIE) properties, and the use of these systems as efficient fluorescent probes for cyanide ions. These conjugated derivatives are linked through a double bond favoring electronic communication, and together with their planar geometry, can strongly aggregate under solvophobic environments, leading to aggregation and exhibiting significant AIE behavior. The double bond between electroactive units is prone to nucleophilic addition reactions by cyanide ions, selectively, conducive to turning off the fluorescence properties, making this hybrid system an efficient probe for cyanide ions. These studies were theoretically explained using DFT and TD-DFT calculations.

| S-EPMC11641556 | biostudies-literature

A cyanide-catalyzed imino-Stetter reaction enables the concise total syntheses of rucaparib.

Project description:Two routes toward the synthesis of rucaparib, an FDA-approved drug used for the treatment of ovarian and prostate cancers, have been developed from commercially available starting materials utilizing the cyanide-catalyzed imino-Stetter reaction as the key step for the construction of the indole motif bearing all the desired substituents in their correct positions. In the first-generation synthesis, meta-fluorobenzoate, the starting material currently used in the process chemistry route of rucaparib, was converted into 4,6-disubstituted 2-aminocinnamic acid derivatives (ester or amide). The cyanide-catalyzed imino-Stetter reaction of aldimines derived from the resulting 2-aminocinnamic acid derivatives and a commercially available aldehyde afforded the desired indole-3-acetic acid derivatives. The final azepinone formation completed the total synthesis of rucaparib in 27% overall yield. To resolve the issues raised in the first-generation synthesis, we further developed a second-generation synthesis of rucaparib. The Heck reaction of a commercially available ortho-iodoaniline derivative with acrylonitrile provided 4,6-disubstituted 2-aminocinnamonitrile, which was subjected to the imino-Stetter reaction with the same aldehyde to provide the desired indole-3-acetonitrile product. Subsequent construction of the azepinone scaffold completed the total synthesis of rucaparib in 59% overall yield over three separation operations. The synthetic strategy reported herein can provide a highly practical route to access rucaparib from commercially available starting materials (5.2% overall yield in the current process chemistry route vs. 59% overall yield in the second-generation synthesis).

| S-EPMC9341288 | biostudies-literature

Mechanistic Studies on Tryptophan Lyase (NosL): Identification of Cyanide as a Reaction Product.

Project description:Tryptophan lyase (NosL) catalyzes the formation of 3-methylindole-2-carboxylic acid and 3-methylindole from l-tryptophan. In this paper, we provide evidence supporting a formate radical intermediate and demonstrate that cyanide is a byproduct of the NosL-catalyzed reaction with l-tryptophan. These experiments require a major revision of the NosL mechanism and uncover an unanticipated connection between NosL and HydG, the radical SAM enzyme that forms cyanide and carbon monoxide from tyrosine during the biosynthesis of the metallo-cluster of the [Fe-Fe] hydrogenase.

| S-EPMC6078386 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data